JP2006016661A - Coated-particulate, cvd system, cvd film deposition method, microcapsule and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a CVD (Chemical Vapor Deposition) system and a CVD film deposition method for uniformly coating the surfaces of particulates or powders with a thin film or ultrafine particulates. <P>SOLUTION: The CVD system comprises: a vessel 2 for placing particulates 1; a chamber 3 for housing the vessel 2; a heater 4 for heating the particulates 1 placed in the vessel 2; and a gas introduction mechanism for introducing a gaseous starting material into the chamber 3, and is characterized in that the surfaces of the particulates 1 are coated with ultrafine particles or a thin film having a particle diameter smaller than that of the particulates. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to coated fine particles, a CVD (chemical vapor deposition) apparatus, a CVD film forming method, a microcapsule, and a manufacturing method thereof. In particular, the present invention relates to coated fine particles, a CVD apparatus, and a CVD film forming method for coating the surface of fine particles with ultrafine particles or a thin film having a smaller particle diameter than the fine particles. The present invention also relates to a microcapsule composed of ultrafine particles or a thin film coated on the surface of fine particles and a method for producing the same.

A conventional sputtering apparatus will be described.
A substrate and a sputtering target are placed facing each other in a vacuum chamber. The sputtering target is attached to the cathode. Then, the vacuum chamber is evacuated to a high vacuum, and argon gas is introduced into the vacuum chamber. When power is supplied to the cathode in this state, glow discharge is generated in the vicinity of the sputtering target, and the generated ions collide with the sputtering target to eject target atoms, and the target material is deposited on the substrate. In this manner, a target material is formed on the substrate (see Patent Document 1).

JP-A-5-171431 (8th to 10th paragraphs, FIG. 3)

  It is also conceivable to form a target material on the surface of the fine particles using the conventional sputtering apparatus. In this case, the fine particles are arranged to face the sputtering target instead of the substrate.

  However, in the above sputtering apparatus, the target material is formed on the surface of the fine particles on the target side in an uneven manner, and the target material is hardly formed on the surface of the fine particles on the side opposite to the target. This is because the atoms ejected from the sputtering target by the sputtering phenomenon have directionality, and the film is formed so that the atoms fall on the surface of the fine particles on the target side.

In the sputtering apparatus, it is also difficult to form a target material in a concave portion of uneven fine particles. This is also because the target atom has directionality.
As described above, in the conventional sputtering apparatus, it is very difficult to coat or cover the entire surface of the fine particles with high uniformity. Therefore, development of a film forming apparatus capable of coating the surface of fine particles with good uniformity is demanded.
Further, the sputtering apparatus has a drawback that the film forming speed is slower than that of the CVD apparatus. When comparing the case where the same thin film is formed with the sputtering apparatus and the case where the film is formed with the CVD apparatus from the viewpoint of the film formation speed, the film formation speed of the sputtering apparatus is about 10 times slower than that of the CVD apparatus.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide coated fine particles in which the surface of fine particles or powder is uniformly coated with a thin film or ultrafine particles. Another object of the present invention is to provide a CVD apparatus and a CVD film forming method capable of coating a thin film or ultrafine particles on the surface of fine particles or powder with good uniformity. Another object of the present invention is to provide a microcapsule comprising ultrafine particles or a thin film coated on the surface of the fine particles and a method for producing the same.

  In order to solve the above problems, attention was paid to a CVD apparatus using chemical vapor deposition. In the case of a CVD apparatus, it is possible to coat the surface of the fine particles with a thin film or ultrafine particles in a state with less bias compared to a sputtering apparatus. The ultrafine particles refer to fine particles having a smaller particle diameter than the fine particles. The state in which the fine particle surface is coated with ultrafine particles includes a state in which the fine particle surface is continuously or discontinuously coated, a state in which the fine particle surface is continuously or discontinuously coated with a collection of ultrafine particles, It includes a state in which ultrafine particles and aggregates of ultrafine particles are mixed and coated continuously or discontinuously.

This will be specifically described below.
The coated fine particles according to the present invention are characterized in that the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles by the CVD method.

  The coated fine particles according to the present invention are obtained by rotating a container having a substantially circular internal cross-sectional shape about a direction perpendicular to the cross section as a rotation axis, while stirring or rotating the fine particles in the container. Is used, and the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles.

  The coated fine particles according to the present invention are obtained by rotating a container having a polygonal cross-sectional shape about a direction perpendicular to the cross-section as a rotation axis, while stirring or rotating the fine particles in the container. Is used, and the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles.

The CVD film forming method according to the present invention contains fine particles in a container,
By using a thermal CVD method or a plasma CVD method, the surface of the fine particles is coated with ultra fine particles or a thin film having a smaller particle diameter than the fine particles.
In the CVD film forming method according to the present invention, fine particles are accommodated in a container whose inner shape of a cross section substantially parallel to the direction of gravity is substantially circular,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has an ultrafine particle smaller than the fine particles. It is characterized by coating fine particles or thin films.

The CVD film forming method according to the present invention accommodates fine particles in a container having a polygonal internal shape of a cross section substantially parallel to the direction of gravity,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has an ultrafine particle smaller than the fine particles. It is characterized by coating fine particles or thin films.

A CVD apparatus according to the present invention includes a container for placing fine particles;
A chamber containing the container;
A heating mechanism for heating the fine particles placed on the container;
A gas introduction mechanism for introducing a source gas into the chamber;
Comprising
By using a thermal CVD method, the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles.

  According to the CVD apparatus, by using the thermal CVD method, the surface of the fine particles or powder can be coated with a thin film or ultra fine particles with higher uniformity than in the conventional sputtering apparatus.

  In the CVD apparatus according to the present invention, the container may be formed integrally with the chamber.

A CVD apparatus according to the present invention is a container that contains fine particles, and a container whose inner shape of a cross section substantially parallel to the direction of gravity is substantially circular;
A rotation mechanism that rotates the container about a direction substantially perpendicular to the cross section as a rotation axis;
A heating mechanism for heating the fine particles contained in the container;
A gas introduction mechanism for introducing a source gas into the container;
Comprising
By using the thermal CVD method while stirring or rotating the fine particles in the container by rotating the container using the rotating mechanism, the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles. It is characterized by doing.

  According to the CVD apparatus, since the internal shape of the container is substantially circular, the powder itself can be rotated and stirred by rotating the container itself. Therefore, it is possible to coat fine particles having a very small particle size with ultrafine particles or a thin film having a smaller particle size than the fine particles with good uniformity.

A CVD apparatus according to the present invention is a container that contains fine particles, and a container having a polygonal internal shape in a cross section substantially parallel to the direction of gravity;
A rotation mechanism that rotates the container about a direction substantially perpendicular to the cross section as a rotation axis;
A heating mechanism for heating the fine particles contained in the container;
A gas introduction mechanism for introducing a source gas into the container;
Comprising
By using the thermal CVD method while stirring or rotating the fine particles in the container by rotating the container using the rotating mechanism, the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles. It is characterized by doing.

  According to the above CVD apparatus, since the container has a polygonal inner shape, the powder itself can be rotated and stirred by rotating the container itself. By making the internal shape of the container polygonal, the powder can be periodically dropped by gravity. For this reason, it is possible to dramatically improve the stirring efficiency as compared with the case where the internal shape of the container is substantially circular, and it is possible to prevent the aggregation of the powder due to moisture or electrostatic force, which is often a problem when handling the powder. . That is, stirring by rotation and pulverization of the agglomerated powder can be performed simultaneously and effectively. Therefore, it is possible to coat fine particles having a very small particle size with ultrafine particles or a thin film having a smaller particle size than the fine particles with good uniformity.

A CVD apparatus according to the present invention includes a container for placing fine particles;
A chamber containing the container;
A gas introduction mechanism for introducing a source gas into the chamber;
An electrode disposed in the chamber and disposed to face the container;
Comprising
By using a plasma CVD method, the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles.

  According to the CVD apparatus, by using the plasma CVD method, the surface of the fine particles or powder can be coated with a thin film or ultrafine particles with higher uniformity than in the conventional sputtering apparatus.

  In the CVD apparatus according to the present invention, the container can be formed integrally with the chamber.

A CVD apparatus according to the present invention is a container that contains fine particles, and a container whose inner shape of a cross section substantially parallel to the direction of gravity is substantially circular;
A rotation mechanism that rotates the container about a direction substantially perpendicular to the cross section as a rotation axis;
An electrode disposed in the container;
A gas introduction mechanism for introducing a source gas into the container;
Comprising
By using the plasma CVD method while stirring or rotating the fine particles in the container by rotating the container using the rotating mechanism, the surface of the fine particles is coated with ultrafine particles or a thin film having a particle diameter smaller than the fine particles. It is characterized by doing.

  According to the CVD apparatus, since the internal shape of the container is substantially circular, the powder itself can be rotated and stirred by rotating the container itself. Therefore, it is possible to coat fine particles having a very small particle size with ultrafine particles or a thin film having a smaller particle size than the fine particles with good uniformity.

A CVD apparatus according to the present invention is a container that contains fine particles, and a container having a polygonal internal shape in a cross section substantially parallel to the direction of gravity;
A rotation mechanism that rotates the container about a direction substantially perpendicular to the cross section as a rotation axis;
An electrode disposed in the container;
A gas introduction mechanism for introducing a source gas into the container;
Comprising
By using the plasma CVD method while stirring or rotating the fine particles in the container by rotating the container using the rotating mechanism, the surface of the fine particles is coated with ultrafine particles or a thin film having a particle diameter smaller than the fine particles. It is characterized by doing.

  According to the above CVD apparatus, since the container has a polygonal inner shape, the powder itself can be rotated and stirred by rotating the container itself. By making the internal shape of the container polygonal, the powder can be periodically dropped by gravity. For this reason, it is possible to dramatically improve the stirring efficiency as compared with the case where the internal shape of the container is substantially circular, and it is possible to prevent the aggregation of the powder due to moisture or electrostatic force, which is often a problem when handling the powder. . That is, stirring by rotation and pulverization of the agglomerated powder can be performed simultaneously and effectively. Therefore, it is possible to coat fine particles having a very small particle size with ultrafine particles or a thin film having a smaller particle size than the fine particles with good uniformity.

Each of the above-described CVD apparatuses according to the present invention preferably further includes a plasma power source connected to one or both of the electrode and the container. The plasma power source may be any one of a high frequency power source, a microwave power source, a DC discharge power source, and a pulse modulated high frequency power source, a microwave power source, and a DC discharge power source.

  In each of the above-described CVD apparatuses according to the present invention, the gas introduction mechanism may have a mechanism for introducing a shower-like gas from the electrode into the container.

  Each of the above-described CVD apparatuses according to the present invention may further include a chamber for housing the container and a vacuum exhaust mechanism for evacuating the chamber. The container may be formed integrally with the chamber. In this case, the chamber is rotated together with the container by a rotation mechanism.

The microcapsule according to the present invention is a microcapsule formed of ultrafine particles or a thin film made of DLC having excellent biocompatibility,
When introduced into the living body or brought into contact with the living body, it has a property that does not impair the original function of the living body or the living body component.

The microcapsule according to the present invention comprises a first ultrafine particle or a first thin film constituting the outer surface,
A microcapsule comprising a second ultrafine particle or a second thin film formed inside the first ultrafine particle or the first thin film,
The first ultrafine particles or the first thin film is made of DLC having excellent biocompatibility,
When introduced into the living body or brought into contact with the living body, it has a property that does not impair the original function of the living body or the living body component.

  The microcapsule according to the present invention is a CVD method in which a container having a substantially circular internal cross-section is rotated about a direction substantially perpendicular to the cross-section as a rotation axis, while stirring or rotating fine particles in the container. The surface of the fine particles is coated with ultrafine particles or a thin film having a particle diameter smaller than that of the fine particles, and the fine particles that are the base of the coated ultrafine particles or thin film are removed. Features.

  The microcapsule according to the present invention is a CVD method in which a container having a polygonal cross-sectional shape is rotated about a direction substantially perpendicular to the cross-section as a rotation axis while stirring or rotating fine particles in the container. The surface of the fine particles is coated with ultrafine particles or a thin film having a particle diameter smaller than that of the fine particles, and the fine particles that are the base of the coated ultrafine particles or thin film are removed. Features.

In each of the above-described microcapsules according to the present invention, the ultrafine particles or the thin film is made of DLC having excellent biocompatibility,
When introduced into the living body or brought into contact with the living body, it preferably has a property that does not impair the original function of the living body or the living body component.

  The microcapsule according to the present invention is a CVD method in which a container having a substantially circular internal cross-section is rotated about a direction substantially perpendicular to the cross-section as a rotation axis, while stirring or rotating fine particles in the container. The first ultrafine particles or the first thin film having a particle diameter smaller than the fine particles are coated on the surfaces of the fine particles, and the first ultrafine particles or the first thin films are coated by using the CVD method. The surface of the thin film is coated with a second ultrafine particle or a second thin film having a particle diameter smaller than that of the fine particle, and becomes a matrix of the coated first and second ultrafine particles or the first and second thin films. It is characterized in that the fine particles are removed.

  The microcapsule according to the present invention is a CVD method in which a container having a polygonal cross-sectional shape is rotated about a direction substantially perpendicular to the cross-section as a rotation axis while stirring or rotating fine particles in the container. The first ultrafine particles or the first thin film having a particle diameter smaller than the fine particles are coated on the surfaces of the fine particles, and the first ultrafine particles or the first thin films are coated by using the CVD method. The surface of the thin film is coated with a second ultrafine particle or a second thin film having a particle diameter smaller than that of the fine particle, and becomes a matrix of the coated first and second ultrafine particles or the first and second thin films. It is characterized in that the fine particles are removed.

Each of the above-described microcapsules according to the present invention is composed of DLC having excellent biocompatibility of the second ultrafine particles or the second thin film,
When introduced into the living body or brought into contact with the living body, it preferably has a property that does not impair the original function of the living body or the living body component.

  In addition, each of the microcapsules according to the present invention described above has a B spectrum as the G peak baseline intensity and a G peak corrected intensity as A in the Raman spectrum obtained as a result of the Raman spectrum analysis of the DLC. The value of / A is preferably less than 1.9.

In the microcapsule according to the present invention, the DLC is preferably formed using a power density of 0.28 W / cm ² or more.

The method for producing a microcapsule according to the present invention contains fine particles in a container having a substantially circular internal shape of a cross section substantially parallel to the direction of gravity,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has an ultrafine particle smaller than the fine particles. Coating fine particles or thin films,
The coated ultrafine particles or the fine particles serving as a matrix of the thin film are removed.

The method for producing a microcapsule according to the present invention contains fine particles in a container whose internal shape of a cross section substantially parallel to the direction of gravity is a polygon,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has an ultrafine particle smaller than the fine particles. Coating fine particles or thin films,
The coated ultrafine particles or the fine particles serving as a matrix of the thin film are removed.

In each of the above-described microcapsule production methods according to the present invention, the ultrafine particles or thin film is composed of DLC having excellent biocompatibility,
When coating the ultrafine particles or thin film, a hydrocarbon-based gas containing at least carbon and hydrogen is introduced into the container under a pressure of 0.5 mTorr or more and 500 mTorr or less, and an electrode connected to a high-frequency power source is disposed in the container. It is also possible to apply a high frequency power having a power density of 0.28 W / cm ² or more to the electrode and coat the electrode by a plasma CVD method.

The method for producing a microcapsule according to the present invention contains fine particles in a container having a substantially circular internal shape of a cross section substantially parallel to the direction of gravity,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has a smaller particle diameter than the fine particles. Coating one ultrafine particle or first thin film;
The fine particles coated with the first ultrafine particles or the first thin film are accommodated in a container whose internal shape of a cross section substantially parallel to the direction of gravity is substantially circular,
By using the CVD method while stirring or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section, the first ultrafine particles or the first thin film Coating the surface with second ultrafine particles or second thin film having a particle diameter smaller than that of the fine particles,
The coated first and second ultrafine particles or the fine particles serving as a matrix of the first and second thin films are removed.

The method for producing a microcapsule according to the present invention contains fine particles in a container whose internal shape of a cross section substantially parallel to the direction of gravity is a polygon,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has a smaller particle diameter than the fine particles. Coating one ultrafine particle or first thin film;
The fine particles coated with the first ultrafine particles or the first thin film are accommodated in a container whose inner shape of a cross section substantially parallel to the direction of gravity is a polygon,
By using the CVD method while stirring or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section, the first ultrafine particles or the first thin film Coating the surface with second ultrafine particles or second thin film having a particle diameter smaller than that of the fine particles,
The coated first and second ultrafine particles or the fine particles serving as a matrix of the first and second thin films are removed.

In each of the above-described microcapsule production methods according to the present invention, the second ultrafine particles or the second thin film is made of DLC having excellent biocompatibility,
When coating the second ultrafine particles or the second thin film, a hydrocarbon-based gas containing at least carbon and hydrogen is introduced into the container under a pressure of 0.5 mTorr or more and 500 mTorr or less and connected to a high frequency power source. It is also possible to dispose the electrode in the container and apply high-frequency power having a power density of 0.28 W / cm ² or more to the electrode to coat the electrode by plasma CVD.

  As described above, according to the present invention, coated fine particles in which the surface of fine particles or powder is coated with a thin film or ultrafine particles with good uniformity can be provided. In addition, according to another aspect of the present invention, it is possible to provide a CVD apparatus and a CVD film forming method that can uniformly coat a surface of fine particles or powder with a thin film or ultra fine particles. According to another aspect of the present invention, a microcapsule composed of ultrafine particles or a thin film coated on the surface of the fine particles and a method for producing the same can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of the present invention will be described below with reference to the drawings.
(Embodiment 1)
FIG. 1 is a block diagram showing an outline of a thermal CVD apparatus according to Embodiment 1 of the present invention. This thermal CVD apparatus is used to coat the surface of fine particles (or powder) with ultra fine particles having a particle diameter smaller than the fine particles (here, ultra fine particles are fine particles having a particle diameter smaller than the fine particles) or a thin film. Device.

  The thermal CVD apparatus has a container 2 on which powder (fine particles) 1 is placed or stored. Below the container 2, a heater 4 is disposed as a heating mechanism for heating the powder 1. The container 2 and the heater 4 are disposed in the chamber 3.

In addition, the thermal CVD apparatus includes a gas introduction mechanism that introduces gas into the chamber 3. The gas introduction mechanism has a first gas introduction mechanism that introduces O ₂ gas and a second gas introduction mechanism that introduces SiH ₄ gas. The first gas introduction mechanism includes pipes 5 to 7, a first valve 12, a first mass flow controller (MFC) 14, and an O ₂ gas supply source. The second gas introduction mechanism has pipes 8 to 10, a second valve 13, a first mass flow controller (MFC) 15, and a SiH ₄ gas supply source.

The front end of the pipe 5 is connected to the chamber 3, and O ₂ gas is ejected from the front end of the pipe 5 into the chamber 3. The base end of the pipe 5 is connected to one side of the first valve 12, and the other side of the first valve 12 is connected to one end of the pipe 6. The other end of the pipe 6 is connected to one end of the mass flow controller 14, and the other end of the mass flow controller 14 is connected to one end of the pipe 7. The other end of the pipe 7 is connected to an O ₂ gas supply source.

The tip of the pipe 8 is connected to the chamber 3, and SiH ₄ gas is jetted from the tip of the pipe 8 into the chamber 3. The base end of the pipe 8 is connected to one side of the second valve 13, and the other side of the second valve 13 is connected to one end of the pipe 9. The other end of the pipe 9 is connected to one end of the mass flow controller 15, and the other end of the mass flow controller 15 is connected to one end of the pipe 10. The other end of the pipe 10 is connected to a SiH ₄ gas supply source.

  The thermal CVD apparatus also includes a vacuum pump 16 that evacuates the inside of the chamber 3. The vacuum pump 16 is connected to the chamber 3 by a pipe 11.

Next, a CVD film forming method for coating the powder (fine particles) 1 with ultrafine particles or a thin film using the thermal CVD apparatus will be described.
First, a powder 1 in which many fine particles are collected is contained in a container 2. The amount of the powder 1 accommodated in the container 2 is preferably such that two to three layers made of fine particles are laminated. This is because if the number of layers of fine particles is increased, the raw material gas for CVD film formation is difficult to reach the fine particles in the lower layer, so that the thin film adheres to the surface of the lower fine particles. The base material constituting the fine particles 1 may be resin, metal or ceramic, and various materials can be used. In this embodiment, for example, Ti powder or Al ₂ O ₃ powder is used. The fine particles 1 do not necessarily have to be composed of a single substance, and can be composed of a mixture of a plurality of substances. Moreover, various shapes can be used as the shape of the fine particles 1, and for example, a sphere or a shape close to a sphere is preferable.

Next, while heating the powder 1 to a predetermined temperature (for example, about 200 ° C.) with the heater 4 through the container 2, a predetermined pressure (for example, about 2 × 10 ⁻³ Torr) is used in the chamber 3 using the vacuum pump 16. ) Until reduced pressure. Then, the oxygen gas whose flow rate was controlled by the mass flow controller 14 by opening the first valve 12 was introduced into the chamber 3 through the pipes 5 to 7, and the flow rate was controlled by the mass flow controller 15 by opening the second valve 13. SiH ₄ gas is introduced into the chamber 3 through the pipes 8 to 10. This makes it possible to cover the ultra-fine particles or thin films made of SiO ₂ on each surface of the fine particles of the powder 1.

FIG. 2 is a cross-sectional view illustrating an example of coated fine particles obtained by coating fine particles with a thin film using the thermal CVD apparatus shown in FIG.
The coated fine particles 18 are obtained by coating the surface of the fine particles 1 with the thin film 17 with good uniformity. However, in the thermal CVD apparatus, since the thin film is formed by the thermal CVD method with the fine particles 1 accommodated in the container 2 kept stationary, the bottom of the fine particles 1 (the portion in contact with the container 2) is covered. The thickness of the thin film is reduced. On the other hand, when a thin film is coated on a fine particle by a conventional sputtering apparatus, the thin film is mainly covered on the upper part of the fine particle (portion on the sputtering target side) because the throwing power is poor compared to the CVD apparatus. The portion and the bottom are not sufficiently covered with the thin film.

According to the first embodiment, by using a thermal CVD apparatus, the surface of fine particles or powder can be coated with a thin film or ultrafine particles with higher uniformity than in a conventional sputtering apparatus.
In this embodiment mode, since a CVD method is used, a fine thin film having better crystallinity than that of a sputtering method can be coated on the fine particles.

(Embodiment 2)
3A is a cross-sectional view schematically showing a thermal CVD apparatus according to Embodiment 2 of the present invention, and FIG. 3B is a cross-section taken along line 3B-3B shown in FIG. FIG. This thermal CVD apparatus is an apparatus for coating the surface of fine particles (or powder) with ultra fine particles or a thin film having a smaller particle diameter than the fine particles.

  The thermal CVD apparatus has a cylindrical chamber 3. Both ends of the chamber 3 are closed by a chamber lid 20. A container 19 is disposed inside the chamber 3. The container 19 has a cylindrical portion (round barrel), and the powder (fine particles) 1 is accommodated inside the round barrel. The cross section shown in FIG. 3B is a cross section substantially parallel to the direction of gravity. In the present embodiment, the container 19 having a substantially circular cross section is used. However, the present invention is not limited to this, and a container having a substantially elliptical cross section can also be used.

  The container 19 is provided with a rotating mechanism (not shown). By rotating the container 19 as indicated by the arrow by this rotating mechanism, the powder (fine particles) 1 in the container 19 is coated while being stirred or rotated. The processing is performed. A rotation axis when the container 19 is rotated by the rotation mechanism is an axis parallel to a substantially horizontal direction (a direction perpendicular to the direction of gravity). A heater 21 is disposed on the outer surface of the container 19 as a heating mechanism for heating the powder 1.

In addition, the thermal CVD apparatus includes a gas introduction mechanism that introduces gas into the container 19. The gas introduction mechanism has a first gas introduction mechanism that introduces O ₂ gas and a second gas introduction mechanism that introduces SiH ₄ gas. The structures of the first gas introduction mechanism and the second gas introduction mechanism are substantially the same as those in the first embodiment. Further, the thermal CVD apparatus includes a vacuum pump (not shown) that evacuates the chamber 3.

Next, a CVD film forming method for coating the powder (fine particles) 1 with ultrafine particles or a thin film using the thermal CVD apparatus will be described.
First, the powder 1 in which many fine particles are collected is accommodated in the container 19. Although various materials can be used as the powder 1, for example, Ti powder or Al ₂ O ₃ powder is used in the present embodiment as in the first embodiment.

Next, while heating the powder 1 to a predetermined temperature (for example, about 200 ° C.) through the container 19 with the heater 4, a predetermined pressure (for example, about 2 × 10 ⁻³ Torr) is used in the chamber 3 using the vacuum pump 16. ) Until reduced pressure. Then, oxygen gas whose flow rate is controlled by the first gas introduction mechanism is introduced into the container 19, and SiH ₄ gas whose flow rate is controlled by the second gas introduction mechanism is introduced into the container 19. Then, by rotating the container 19 at a predetermined rotation speed (for example, 15 rpm) for a predetermined time (for example, 120 minutes) by the rotation mechanism, the powder 1 in the container 19 is rotated and stirred. As a result, the surface of each fine particle of the powder 1 can be coated with ultrafine particles or a thin film made of a SiO ₂ film with good uniformity.

In the second embodiment, the same effect as in the first embodiment can be obtained.
Further, according to the present embodiment, since the powder itself can be rotated and stirred by rotating the container 19 itself of the round barrel, the powder agglomerates due to moisture or electrostatic force, which is often a problem when handling the powder. Can be prevented. Therefore, it is possible to coat fine particles having a very small particle size with ultrafine particles or a thin film having a smaller particle size than the fine particles with good uniformity.

(Embodiment 3)
4A is a cross-sectional view schematically showing a thermal CVD apparatus according to Embodiment 3 of the present invention, and FIG. 4B is a cross section taken along line 4B-4B shown in FIG. 4A. FIG. 4, the same parts as those in FIG. 3 are denoted by the same reference numerals, and the description of the same parts is omitted.

  A container 22 is disposed inside the chamber 3. The container 22 has a hexagonal barrel shape (hexagonal barrel shape) as shown in FIG. The powder (fine particles) 1 is accommodated inside the container 22. The cross section shown in FIG. 4B is a cross section substantially parallel to the direction of gravity. In the present embodiment, the hexagonal barrel-shaped container 22 is used. However, the present invention is not limited to this, and a polygonal barrel-shaped container other than a hexagon can also be used.

  The container 22 is provided with a rotation mechanism (not shown) as in the second embodiment. By rotating the container 22 as shown by the arrow by this rotating mechanism, the coating process is performed while stirring or rotating the powder (fine particles) 1 in the container 22. A rotation axis when the container 22 is rotated by the rotation mechanism is an axis parallel to a substantially horizontal direction (a direction perpendicular to the gravity direction).

In addition, a heating mechanism is disposed on the outer surface of the container 22 as in the second embodiment. The thermal CVD apparatus includes a gas introduction mechanism and a vacuum pump as in the second embodiment.

Next, a CVD film forming method for coating the powder (fine particles) 1 with ultrafine particles or a thin film using the thermal CVD apparatus will be described.
First, the powder 1 in which many fine particles are collected is accommodated in the container 19. Although various materials can be used as the powder 1, for example, Ti powder or Al ₂ O ₃ powder is used in the present embodiment as in the first embodiment.

Next, while heating the powder 1 to a predetermined temperature via the container 22 with the heater 4, the inside of the chamber 3 is depressurized to a predetermined pressure using a vacuum pump. Then, oxygen gas whose flow rate is controlled by the first gas introduction mechanism is introduced into the container 22, and SiH ₄ gas whose flow rate is controlled by the second gas introduction mechanism is introduced into the container 22. Then, the powder 1 in the container 22 is rotated and stirred by rotating the container at a predetermined rotation speed for a predetermined time by the rotation mechanism. As a result, the surface of each fine particle of the powder 1 can be coated with ultrafine particles or a thin film made of a SiO ₂ film with good uniformity.

FIG. 5 is a sectional view showing an example of coated fine particles obtained by coating fine particles with a thin film by the thermal CVD apparatus shown in FIG.
The coated fine particles 23 are obtained by coating the surface of the fine particles 1 with the thin film 17 with good uniformity. In the thermal CVD apparatus, since the thin film is formed by the thermal CVD method while rotating and stirring the container 22 by rotating the container 22, the entire surface of the fine particle 1 is coated with a very uniform thickness. Can do. Even when the surface of the fine particles 1 has irregularities or depressions, the thin film can be coated with good coverage on the irregularities or depressions due to the characteristics of the CVD apparatus that the film is well attached. On the other hand, when a thin film is coated on fine particles having irregularities or depressions by a conventional sputtering apparatus, the irregularities or depressions are not sufficiently covered with the thin film because the throwing power is poor compared to the CVD apparatus.

In the third embodiment, the same effect as in the first embodiment can be obtained.
In addition, according to the present embodiment, the powder itself can be rotated and stirred by rotating the hexagonal barrel-shaped container 22 itself, and further, the powder can be periodically removed by gravity by making the barrel hexagonal. Can be dropped. For this reason, it is possible to dramatically improve the stirring efficiency as compared with the second embodiment, and it is possible to prevent aggregation of the powder due to moisture or electrostatic force, which is often a problem when handling the powder. That is, stirring by rotation and pulverization of the agglomerated powder can be performed simultaneously and effectively. Therefore, it is possible to coat fine particles having a very small particle size with ultrafine particles or a thin film having a smaller particle size than the fine particles with good uniformity. Specifically, it is possible to coat ultrafine particles or a thin film on fine particles having a particle size of 50 μm or less.

(Embodiment 4)
FIG. 6 is a block diagram showing an outline of a plasma CVD apparatus according to the fourth embodiment of the present invention. This plasma CVD apparatus is an apparatus for coating the surface of fine particles (or powder) with ultra fine particles or a thin film having a smaller particle diameter than the fine particles.

  The plasma CVD apparatus has a chamber 3. In the chamber 3, a container 2 for storing powder (fine particles) 1 to be coated is arranged. The container 2 is connected to a plasma power source 31 or a ground potential, and both can be switched by a switch 32.

Further, the plasma CVD apparatus includes a source gas introduction mechanism that introduces a source gas into the chamber 3. This source gas introduction mechanism has a cylindrical gas shower electrode 24, and this gas shower electrode 24 is arranged in the chamber 3. On one side of the gas shower electrode 24, a plurality of gas outlets for blowing out one or more source gases in a shower shape are formed. The gas outlet is disposed so as to face the powder 1 accommodated in the container. The other side of the gas shower electrode 24 is connected to one side of a mass flow controller (MFC) 27 via a vacuum valve 26. The other side of the mass flow controller 27 is connected to the source gas generation source 28 through a vacuum valve and a filter (not shown). The source gas generation source 28 is different in the kind of source gas generated depending on the thin film coated on the powder. For example, when a SiO ₂ film is formed, SiH ₄ gas or the like is generated.

Further, the plasma CVD apparatus is provided with a plasma power supply mechanism, and this plasma power supply mechanism has a plasma power source 25 connected to the gas shower electrode 24 via a switch 33. The plasma power supplies 25 and 31 are any one of a high-frequency power supply for supplying high-frequency power (RF output), a microwave power supply, a DC discharge power supply, and a pulse-modulated high-frequency power supply, a microwave power supply, and a DC discharge power supply. If it is. For example, when the plasma power supply supplies high frequency power, it is preferable to arrange an impedance matching unit (matching box) (not shown) between the high frequency power supply and the gas shower electrode 24. That is, in this case, the gas shower electrode 24 is connected to a matching box, and the matching box is connected to a high frequency power source (RF power source) via a coaxial cable.
The plasma power source may be connected to one of the gas shower electrode 24 and the container 2 and the ground potential may be connected to the other, or the plasma power source may be connected to both the gas shower electrode 24 and the container 2. Also good.

  In addition, the plasma CVD apparatus includes a vacuum exhaust mechanism that exhausts the inside of the chamber 3. For example, the gas shower electrode 12 is provided with a plurality of exhaust ports (not shown) for exhausting the inside of the chamber 3, and the exhaust ports are connected to a vacuum pump (not shown).

Next, a method for coating the powder 1 with ultrafine particles or a thin film using the plasma CVD apparatus will be described.
First, the powder 1 composed of a plurality of fine particles is accommodated in the container 2. The amount of the powder 1 accommodated in the container 2 and the material of the powder are the same as those in the first embodiment. Thereafter, the inside of the chamber 3 is depressurized to a predetermined pressure (for example, about 2 × 10 ⁻³ Torr) by operating a vacuum pump.

Next, the vacuum valve 26 is opened, a raw material gas (for example, SiH ₄ gas) is generated at the raw material gas generation source 28, the flow rate of this raw material gas is controlled by the mass flow controller 27, and the flow rate controlled raw material gas is supplied to the gas shower electrode 24. Introduce inside. And source gas is blown out from the gas blower outlet of a gas shower electrode.

Thereafter, an RF output of 13.56 MHz, for example, is supplied to the gas shower electrode 24 from a high frequency power source (RF power source) which is an example of the plasma power source 25 via, for example, a matching box. At this time, the container 2 is connected to the ground potential. Thereby, plasma is ignited between the gas shower electrode 24 and the container 2. At this time, the matching box is matched with the impedance of the container 2 and the gas shower electrode 24 by the inductance L and the capacitance C. As a result, plasma is generated in the chamber 3 and the surface of the fine particles 1 is coated with ultrafine particles or thin film made of SiO ₂ .

  According to Embodiment 4 described above, by using a plasma CVD apparatus, the surface of fine particles or powder can be coated with a thin film or ultrafine particles with higher uniformity than in a conventional sputtering apparatus.

In this embodiment mode, since the plasma CVD method is used, the surface of the fine particles can be coated with a thin film or the like even at a low temperature of 100 ° C. or lower. Therefore, a thin film or the like can be coated on fine particles that are easily decomposed at a high temperature of 100 ° C. or more, fine particles that easily undergo phase change, or fine particles that are easily surface-modified.
In this embodiment, since a plasma CVD apparatus is used, target replacement is not necessary and maintenance is good as compared with the case of using a sputtering apparatus.

(Embodiment 5)
FIG. 7A is a sectional view schematically showing a plasma CVD apparatus according to the fifth embodiment of the present invention, and FIG. 7B is a sectional view taken along line 7B-7B shown in FIG. FIG. This plasma CVD apparatus is an apparatus for coating the surface of fine particles (or powder) with ultra fine particles or a thin film having a smaller particle diameter than the fine particles.

  The plasma CVD apparatus has a cylindrical chamber 3. Both ends of the chamber 3 are closed by a chamber lid 20. A container 29 is disposed inside the chamber 3. The container 29 has a cylindrical portion (round barrel), and the powder (fine particles) 1 as a coating object is accommodated inside the round barrel. The container 29 also functions as an electrode and is connected to a plasma power source 31 or a ground potential, and both can be switched by a switch 32. The cross section shown in FIG. 7B is a cross section substantially parallel to the direction of gravity. In the present embodiment, the container 29 having a substantially circular cross section is used. However, the present invention is not limited to this, and a container having a substantially elliptical cross section may be used.

  The container 29 is provided with a rotating mechanism (not shown), and the rotating mechanism rotates the container 29 as indicated by the arrow with the gas shower electrode 24 as the center of rotation, thereby allowing the powder (fine particles) in the container 29 to be rotated. The coating process is performed while stirring or rotating 1. A rotation axis when the container 29 is rotated by the rotation mechanism is an axis parallel to a substantially horizontal direction (a direction perpendicular to the direction of gravity). Further, the airtightness in the chamber 3 is maintained even when the container 29 is rotated.

  Further, the plasma CVD apparatus includes a source gas introduction mechanism that introduces a source gas into the chamber 3. This source gas introduction mechanism has a cylindrical gas shower electrode 24, and this gas shower electrode 24 is arranged in a container 29. That is, an opening is formed on one side of the container 29, and the gas shower electrode 24 is inserted from this opening. The gas shower electrode 24 is formed with a plurality of gas outlets for blowing out one or more source gases in a shower shape. The gas outlet is disposed so as to face the powder 1 accommodated in the container. The gas outlet is arranged in a direction of about 1 ° to 90 ° in the rotation direction of the container 29 with respect to the gravity direction 30 as shown in FIG.

As in the fourth embodiment, the gas shower electrode 24 is connected to a vacuum valve, a mass flow controller (MFC), a vacuum valve, a filter, and a source gas generation source (not shown). The source gas generation source differs in the type of source gas generated depending on the thin film coated on the powder. For example, when a SiO ₂ film is formed, SiH ₄ gas or the like is generated.

  In addition, the plasma CVD apparatus includes a plasma power supply mechanism, and this plasma power supply mechanism has the same structure as that of the fourth embodiment. In addition, the plasma CVD apparatus includes a vacuum exhaust mechanism that exhausts the inside of the chamber 3 and the structure of the vacuum exhaust mechanism is substantially the same as that of the fourth embodiment.

Next, a method for coating the powder 1 with ultrafine particles or a thin film using the plasma CVD apparatus will be described.
First, the powder 1 composed of a plurality of fine particles is accommodated in the container 2. Although various materials can be used as the powder 1, for example, Ti powder or Al ₂ O ₃ powder is used in the present embodiment as in the first embodiment. Thereafter, the inside of the chamber 3 is depressurized to a predetermined pressure (for example, about 2 × 10 ⁻³ Torr) by operating a vacuum pump. At the same time, the container 29 is rotated by the rotation mechanism, so that the powder (fine particles) 1 accommodated in the container 29 moves on the inner surface of the container while rolling between the gravitational direction 30 and 90 ° in the rotational direction.

Next, a source gas (for example, SiH ₄ gas) is generated in the source gas generation source, the flow rate of the source gas is controlled by a mass flow controller, and the source gas whose flow rate is controlled is introduced into the gas shower electrode 24. And source gas is blown out from the gas blower outlet of a gas shower electrode. As a result, the raw material gas is sprayed onto the fine particles 1 moving while rolling in the container 29, and the pressure suitable for film formation by the CVD method is maintained by the balance between the controlled gas flow rate and the exhaust capability.

Thereafter, an RF output of 13.56 MHz, for example, is supplied to the gas shower electrode 24 from a high frequency power source (RF power source) which is an example of the plasma power source 25 via, for example, a matching box. At this time, the container 29 is connected to the ground potential. Thereby, plasma is ignited between the gas shower electrode 24 and the container 29. At this time, the matching box is matched with the impedance of the container 2 and the gas shower electrode 24 by the inductance L and the capacitance C. Thereby, plasma is generated in the container 29, ultra-fine particles or thin films made of SiO ₂ is coated on the surface of the microparticle 1. That is, since the fine particles 1 are rolled by rotating the container 29, it is possible to easily coat the entire surface of the fine particles 1 with a thin film.

In the fifth embodiment, the same effect as in the fourth embodiment can be obtained.
Further, according to the present embodiment, since the powder itself can be rotated and stirred by rotating the container 29 itself of the round barrel, the powder agglomeration due to moisture or electrostatic force, which is often a problem when handling the powder. Can be prevented. Therefore, it is possible to coat fine particles having a very small particle size with ultrafine particles or a thin film having a smaller particle size than the fine particles with good uniformity.

(Embodiment 6)
FIG. 8A is a sectional view schematically showing a plasma CVD apparatus according to the sixth embodiment of the present invention, and FIG. 8B is a sectional view taken along line 8B-8B shown in FIG. FIG. 8, the same parts as those in FIG. 7 are denoted by the same reference numerals, and the description of the same parts is omitted.

  A container 30 is disposed inside the chamber 3. As shown in FIG. 8B, the container 30 has a hexagonal barrel shape (hexagonal barrel shape) in cross section. And inside the container 30, the powder (fine particle) 1 which is a coating target object is accommodated. The container 30 also functions as an electrode and is connected to a plasma power source 31 or a ground potential, and both can be switched by a switch 32. The cross section shown in FIG. 8B is a cross section substantially parallel to the direction of gravity. In the present embodiment, the hexagonal barrel-shaped container 30 is used. However, the present invention is not limited to this, and a polygonal barrel-shaped container other than a hexagon can also be used.

  The container 30 is provided with a rotation mechanism (not shown) as in the fifth embodiment. By rotating the container 30 as indicated by an arrow by this rotating mechanism, the coating process is performed while stirring or rotating the powder (fine particles) 1 in the container 30. A rotation axis when the container 30 is rotated by the rotation mechanism is an axis parallel to a substantially horizontal direction (a direction perpendicular to the direction of gravity).

  Further, the plasma CVD apparatus includes a source gas introduction mechanism and a vacuum exhaust mechanism as in the fifth embodiment. This source gas introduction mechanism has a cylindrical gas shower electrode 24 as in the fifth embodiment. The plasma CVD apparatus is provided with a plasma power supply mechanism as in the fifth embodiment.

Next, a CVD film forming method for coating powder (fine particles) 1 with ultrafine particles or a thin film using the plasma CVD apparatus will be described.
First, the powder 1 composed of a plurality of fine particles is accommodated in the container 30. Although various materials can be used as the powder 1, for example, Ti powder or Al ₂ O ₃ powder is used in the present embodiment as in the first embodiment. Thereafter, the inside of the chamber 3 is depressurized to a predetermined pressure (for example, about 2 × 10 ⁻³ Torr) by operating a vacuum pump. At the same time, the container 30 is rotated by the rotation mechanism, whereby the powder (fine particles) 1 accommodated therein is stirred or rotated on the inner surface of the container.

Next, a source gas (for example, SiH ₄ gas) is generated in the source gas generation source, the flow rate of the source gas is controlled by a mass flow controller, and the source gas whose flow rate is controlled is introduced into the gas shower electrode 24. And source gas is blown out from the gas blower outlet of a gas shower electrode. As a result, the raw material gas is sprayed onto the fine particles 1 moving while stirring or rotating in the container 30, and the pressure suitable for film formation by the CVD method is maintained by the balance between the controlled gas flow rate and the exhaust capability.

Thereafter, an RF output of 13.56 MHz, for example, is supplied to the gas shower electrode 24 from a high frequency power source (RF power source) which is an example of the plasma power source 25 via, for example, a matching box. At this time, the container 30 is connected to the ground potential. Thereby, plasma is ignited between the gas shower electrode 24 and the container 30. At this time, the matching box is matched with the impedance of the container 2 and the gas shower electrode 24 by the inductance L and the capacitance C. As a result, plasma is generated in the container 30, and the surface of the fine particles 1 is coated with ultrafine particles or a thin film made of SiO ₂ . That is, since the fine particles 1 are stirred and rotated by rotating the container 30, it is easy to uniformly coat the thin film on the entire surface of the fine particles 1.

In the sixth embodiment, the same effect as in the fourth embodiment can be obtained.
Further, according to the present embodiment, the powder itself can be rotated and agitated by rotating the hexagonal barrel-shaped container 30 itself, and the powder can be periodically removed by gravity by making the barrel hexagonal. Can be dropped. For this reason, it is possible to dramatically improve the stirring efficiency as compared with the fifth embodiment, and it is possible to prevent aggregation of the powder due to moisture or electrostatic force, which is often a problem when handling the powder. That is, stirring by rotation and pulverization of the agglomerated powder can be performed simultaneously and effectively. Therefore, it is possible to coat ultrafine particles or a thin film having a particle size much smaller than that of the fine particles having a very small particle size. Specifically, it is possible to coat ultrafine particles or a thin film on fine particles having a particle size of 50 μm or less.

(Embodiment 7)
A microcapsule according to Embodiment 7 of the present invention will be described.
The first microcapsule is obtained by coating ultrafine particles or a thin film made of DLC having excellent biocompatibility on the surface of the fine particles, and removing the coated fine particles or the fine particles that are the matrix of the thin film. is there. Another example of the second microcapsule is that the surface of the fine particles is coated with the first ultrafine particles or the first thin film, and the surface of the first ultrafine particles or the first thin film is excellent in biocompatibility. The second ultrafine particles or the second thin film made of DLC having the above were coated, and the coated first and second ultrafine particles or the fine particles serving as the matrix of the first and second thin films were removed. Is. Such a microcapsule is applied to drug delivery as a medicine. The DLC (Diamond Like Carbon) film is an amorphous carbon mainly composed of SP ³ bonds between carbons. It is a hard carbon film that is extremely hard, excellent in insulation, has a high refractive index, and has a very smooth morphology. is there.

  The ultrafine particles or thin film (hereinafter referred to as DLC film) made of DLC is an amorphous carbon-based thin film mainly composed of carbon, and a Raman spectrum curve obtained by synthesizing two or more curves having a mountain shape. It includes those that are relatively soft to very hard. This Raman spectrum is as shown in FIG. However, the Raman spectrum shown in FIG. 9 is merely an example.

  As shown in FIG. 9, the Raman spectrum curve 110 has two peaks called a G band and a D band, and a wave-shaped curve (G band) 111 with a wave number having a peak in the vicinity of 1500. And a mountain-shaped curve (D band) 112 having a peak near 1300 in wave number.

  The DLC film having excellent biocompatibility has a property that when the DLC film is introduced into the living body or brought into contact with the living body, the original function of the living body or the biological component is not impaired. Yes, it has the property of almost no cytotoxicity.

  Here, being excellent in biocompatibility means being excellent in tissue compatibility, excellent in nonimmunity, and excellent in blood compatibility.

Tissue compatibility means that when a DLC membrane is introduced into a living body or brought into contact with a living body, no damage is caused to cells constituting the tissue of the living body. In other words, it does not cause cytotoxicity.
Cytotoxicity means that originally proliferating / differentiating cells are directly or indirectly brought into contact with certain substances and destroyed.

Non-immunity means that when a DLC film is introduced into a living body or brought into contact with a living body, an immune reaction that protects the living body from stimuli (harmful foreign substances) from outside the living body is not induced.
The blood compatibility means that unnecessary use of blood coagulation (thrombus formation) or destruction (hemolysis) does not occur when the DLC film is used at a site in contact with blood. There are several factors in blood coagulation, one of which is platelet adsorption. Since the surface of the material on which albumin in the blood is adsorbed hardly adsorbs platelets, thrombus formation is suppressed.

  Next, a cell experiment for confirming that the DLC film has biocompatibility was performed, which will be described.

The experimental method will be described.
First, a polystyrene dish for culturing cells is prepared. This dish has a square shape in the plane, and is provided with 96 holes (dents) in total of 8 rows and 12 rows, and the culture medium and cells are put into these holes to culture the cells. Is. The bottom (bottom) of these holes is subjected to the following treatment. That is, C ₇ H ₈ used gas, gas flow rate of 20 sccm, gas pressure of 5 mmTorr, RF output of the following A to I and a DLC film coated on the bottom of the film with a film formation time, as is polystyrene (PS) , 8 pieces each subjected to TCD (tissue culture polystyrene dish) treatment are provided. TCD is a tissue culture dish.

Film formation condition A: RF output of 300 W, film formation time of 30 seconds Film formation condition B: RF output of 300 W, film formation time of 60 seconds Film formation condition C: RF output of 300 W, film formation time of 90 seconds Condition D: 500 W RF output, 30 second film formation time Film formation condition E: 500 W RF output, 60 second film formation time Film formation condition F: 500 W RF output, 90 second film formation time Film formation condition G : RF output of 900 W, film formation time of 30 seconds Film formation condition H: RF output of 900 W, film formation time of 60 seconds Film formation condition I: RF output of 900 W, film formation time of 90 seconds

  Next, the cells were prepared in a medium, and the cell suspension was placed in each hole of the dish. After incubation for 24 hours, cell adhesion evaluation and cytotoxicity evaluation were performed on the bottom surface of the hole. As the cells, rat calvaria-derived osteoblasts (cells from the bone at the top of the mouse) are used, and as the medium, media such as DMEM medium, 10% FBS (serum), antibiotics, and non-essential amino acids are necessary. Use nutrients.

A cell adhesion test for evaluating cell adhesion will be described.
First, rat calvaria-derived osteoblasts are adjusted to 8 × 10 ⁴ cells / ml with DMEM medium, and 100 μl of this cell suspension is placed in each well of the dish. Then, after 24 hours of incubation, the number of cells adhering to the bottom surface of the hole was calculated by MTT assay.

  MTT is changed to formazan by enzymes in mitochondria. Mitochondrial activity can be evaluated by dissolving Formazan and performing colorimetric determination. Since the amount of generated formazan is proportional to the number of living cells, the value of MTT assay absorbance (OD 595 nm) is used as the number of adherent cells. That is, since there is one mitochondria per cell, the number of adherent cells can be measured by the number of mitochondria measured from the absorbance value of MTT assay. The result is shown in FIG.

  FIG. 10 shows the results of cell adhesion evaluation, and is a bar graph showing the relationship between PS (polystyrene), DLC-coated AI and TCD in a dish, and the absorbance (OD 595 nm). FIG. 10 shows that the higher the value on the vertical axis, the greater the number of cells attached, but A to I are clearly better in cell adhesion than PS not coated with DLC. there were. Moreover, the cell adhesion was slightly better than the TCD used as a target comparison.

A cytotoxicity test for evaluating cytotoxicity will be described.
First, rat calvaria-derived osteoblasts are adjusted to 8 × 10 ⁴ cells / ml with DMEM medium, and 100 μl of this cell suspension is placed in each well of the dish. Then, after 24 hours of incubation, cytotoxicity was quantitatively measured by the LDH leakage measurement method which is a cell membrane damage test.

LDH, a lysosomal enzyme, is released from the cell into the medium when the cell membrane is damaged. The released LDH was colorimetrically quantified for absorbance (OD 595 nm) using Iatrozyme LDH-L _Q Kit. It can be said that the higher the LDH elution rate, the greater the damage to the cell membrane, and the stronger the cytotoxicity. The test results are shown in FIG.

  FIG. 11 shows the results of cytotoxicity evaluation, and is a bar graph showing the relationship between the elution rate of LDH and PS (polystyrene), A to I and TCD coated with DLC in a dish.

  In FIG. 11, the higher the value of LDH elution rate on the vertical axis, the higher the damage to the cell membrane (that is, the greater the damage to the cell membrane). In the untreated PS that is not coated with DLC, the LDH elution rate is as high as 20%, and it can be said that the disorder of the cell membrane is high. However, since A to I coated with DLC show a low LDH elution rate, it can be said that the damage of the cell membrane is low. Therefore, by coating DLC, the disorder of the cell membrane can be suppressed. AI were clearly less toxic compared to PS without DLC coating. Moreover, the cytotoxicity was almost equivalent to the TCD used as a subject comparison.

  As a result of cell adhesion evaluation and cytotoxicity evaluation, DLC-coated dishes in the dish have the same or higher cell adhesion as TCD and low cytotoxicity regardless of the DLC film thickness. It has been found. Therefore, it can be said that the DLC film is very excellent in biocompatibility. In addition, since the film thickness dependency is not observed, if a DLC film is coated even slightly on the PS surface, it can be a good place for proliferation for osteoblasts.

  Next, an experiment for confirming that the DLC film has blood compatibility was performed, which will be described.

The experimental method will be described.
First, a polystyrene dish is prepared. This dish is the same as that used in the cell experiment described above.
Next, the protein solution is put into each hole of the dish, and the protein adsorbed on the bottom surface of the hole is detected using an enzyme immunoassay (ELISA method). The ELISA method is an abbreviation of enzyme-liked immunosorbent assay, which tracks enzyme activity and quantifies the amount of antigen or antibody, and has extremely high detection sensitivity and is in nanogram order. Can be detected.

  A specific experimental method will be described. Human serum albumin solution adjusted to 500 ng / ml is placed in various dishes, and incubated at 37 ° C. for 1 hour to adsorb albumin to the dish. After 1 hour, the supernatant is removed, the primary antibody solution is added, and the mixture is incubated at 37 ° C. for 2 hours to bind the primary antibody to the adsorbed protein. Thereafter, the dish is washed to remove excess primary antibody.

  Next, the secondary antibody solution is put in a dish and incubated at 37 ° C. for 2 hours to bind the secondary antibody to the primary antibody bound to the protein. Then, as in the case of the primary antibody, excess secondary antibody was washed away and then reacted with alkaline phosphatase bound to the secondary antibody with p-nitrophenyl phosphate disodium hexahydrate. Thereafter, the reaction is stopped with an aqueous sodium hydroxide solution and the absorbance is measured. From the measurement results, protein adsorption rates in various dishes were calculated, and the results are shown in FIG.

  FIG. 12 is a bar graph showing the protein adsorption rate of the bottom part of the hole in the dish (PS (polystyrene), A to I coated with DLC, and TCD). The protein adsorption rate here is the ratio (%) that the protein contained in the protein solution put in the hole is adsorbed on the bottom surface of the hole.

  According to FIG. 12, A to I have a very high protein adsorption rate of 90 to 100%, indicating a very high adsorption rate compared to TCD. From these results, it was confirmed that the DLC membrane had very good blood compatibility.

Next, the results of Raman spectrum analysis performed on the DLC film will be described.
A substrate was fixed on an electrode connected to a high-frequency power source, high-frequency power was applied to this electrode, and a DLC film was formed on the substrate surface by a plasma CVD method to produce a sample. As film formation conditions at this time, C ₇ H ₈ was used as the gas used, the gas flow rate was set to 15 sccm, the gas pressure was set to 5 mTorr, and the RF output was changed from 100 W to 900 W. A Raman spectrum analysis was performed on each sample thus prepared. In the Raman spectrum curve of each sample obtained as a result, the G peak baseline intensity B and the intensity A after G peak correction were measured, and the value of B / A was calculated for each sample. The result is shown in FIG.

  Here, the B / A value is a value of B / A when the G peak baseline intensity is B and the G peak corrected intensity is A, as shown in FIG. FIG. 14 is a Raman spectrum curve for explaining the definition of the B / A value.

FIG. 13 is a graph showing the relationship between the RF output and the B / A value when each sample is manufactured. FIG. 15 is a graph showing the relationship between the RF output and the density of the DLC film when each sample is manufactured. The flow rate of C ₇ H ₈ gas for producing each sample is 15 sccm, and the gas pressure is 5 mTorr.
As shown in FIG. 13, the B / A value of a sample formed with an RF output of 100 W or more is about 1.9, but the B / A value suddenly decreases from an RF output of 200 W, and is 300 W or more. The B / A value at RF output is approximately 1.6 or less. Further, as shown in FIG. 15, the higher the RF output, the higher the density of the DLC film. From the results of FIG. 13 and FIG. 15, the lower the B / A value, the higher the density of the DLC film and the more dense the film is formed. Therefore, the lower the B / A value, the better the DLC film having better biocompatibility. Become. Therefore, in order for the DLC film to be excellent in biocompatibility, it is preferable that the B / A value is less than 1.9.

Next, the result of anodic polarization measurement performed on the DLC film will be described.
A sample was prepared by fixing a Si substrate on an electrode connected to a high-frequency power source, applying high-frequency power to this electrode, and forming a DLC film on the surface of the Si substrate by plasma CVD. As the film forming conditions at this time, C ₇ H ₈ was used as the gas used, and the RF output was changed from 100 W to 500 W. Each sample thus prepared was immersed in a 10% KOH solution, and anodic polarization measurement was performed. The results are shown in FIGS.

FIG. 16 is a graph showing the relationship between the potential and the current density, showing the anodic polarization measurement result of the sample in which the DLC film is formed with the RF output of 100 W.
FIG. 17 is a graph showing the relationship between the potential and the current density, showing the anodic polarization measurement result of the sample in which the DLC film is formed with the RF output of 200 W.
FIG. 18 is a graph showing the relationship between the potential and the current density, showing the anodic polarization measurement result of the Si substrate on which no DLC film is formed.

As a result of the anodic polarization measurement, as shown in FIG. 16, the sample DLC film formed with an RF output of 100 W shows a small active state regardless of the gas flow rate and the gas pressure, and some dissolution of the Si substrate is observed. It was. On the other hand, as shown in FIG. 17, the DLC film of the sample formed with an RF output of 200 W or more had a natural electrode potential shifted to the noble side, and no active state was generated. The critical passivation current density Icrit of the film formed with an RF output of 200 W or more is 3 to 5 orders of magnitude smaller than that of the Si substrate shown in FIG. 18, and the defect area of the DLC film was calculated to be 10 ⁻² to It was confirmed that the film quality was low on the order of 10 ⁻⁵ . Therefore, since a DLC film formed with an RF output of 200 W or more has very low defects, it is possible to protect the base metal from corrosion even if such a DLC film coated with the base metal is embedded in the living body. It becomes possible. Therefore, such a DLC film formed with an RF output of 200 W or higher, in other words, a power density of 0.28 W / cm ² or higher, is preferably used for medical instruments, artificial organs, and the like. Since the RF output electrode area is 708 cm ² (Φ300 mm), the power density of 200 W is 0.28 W / cm ² .

Next, the manufacturing method of the first microcapsule described above will be described.
Using the plasma CVD apparatus shown in FIG. 8, the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles by the method described in Embodiment 6. At this time, ultrafine particles or thin film materials suitable for use as microcapsules are used. For example, NaCl is used as the fine particles, and DLC is used as the material of the ultrafine particles or thin film.

  Specifically, a plurality of NaCl fine particles 1 are accommodated in the container 30. Next, the chamber 3 is depressurized to a predetermined pressure by operating a vacuum pump. At the same time, the container 30 is rotated by the rotation mechanism, whereby the powder (NaCl fine particles) 1 accommodated therein is stirred or rotated on the inner surface of the container.

  Next, a source gas (for example, a hydrocarbon gas containing carbon and hydrogen) is generated in the source gas generation source, the flow rate of the source gas is controlled by a mass flow controller, and the source gas whose flow rate is controlled is supplied to the gas shower electrode 24. Introduce inside. And source gas is blown out from the gas blower outlet of a gas shower electrode. The gas pressure at this time is 0.5 mTorr or more and 500 mTorr or less. As a result, the raw material gas is sprayed onto the fine particles 1 moving while stirring or rotating in the container 30, and the pressure suitable for film formation by the CVD method is maintained by the balance between the controlled gas flow rate and the exhaust capability.

  Thereafter, an RF output of 13.56 MHz, for example, is supplied to the gas shower electrode 24 from a high frequency power source (RF power source) which is an example of the plasma power source 25 via, for example, a matching box. At this time, the RF output is 30 W or more, and the container 30 is connected to the ground potential. Thereby, plasma is ignited between the gas shower electrode 24 and the container 30. As a result, plasma is generated in the container 30 and the surface of the NaCl fine particles 1 is coated with ultrafine particles or thin films made of DLC. That is, since the fine particles 1 are stirred and rotated by rotating the container 30, it is possible to easily coat the entire surface of the fine particles 1 with a thin film or the like.

  Thereafter, the coated ultrafine particles or the NaCl fine particles serving as the base of the thin film are removed by dissolution, vaporization or the like. In detail, for example, water is put into a beaker, and NaCl fine particles coated with DLC are put into this water. At this time, the NaCl fine particles coated with DLC sink to the bottom of the water.

  Next, as time passes, the DLC-coated fine particles gradually float on the water surface. This is because the base NaCl fine particles are dissolved in water and removed from the coated DLC.

  Then, after a certain period of time, all the fine particles coated with DLC float on the water surface. In this way, the NaCl in all the fine particles coated with DLC is removed, and microcapsules are produced.

Next, a method for manufacturing the above-described second microcapsule will be described.
Using the plasma CVD apparatus shown in FIG. 8, the surface of the fine particles is coated with the first ultrafine particles or the first thin film having a particle diameter smaller than that of the fine particles by the method described in Embodiment 6. At this time, the material of the first ultrafine particles or the first thin film may be a metal or an insulator as long as it is suitable for use as a microcapsule. Next, by using the plasma CVD apparatus shown in FIG. 8, the first ultrafine particles or second ultrafine particles having a smaller particle diameter than the fine particles are formed on the surface of the first ultrafine particles or the first thin film by the method described in Embodiment 6. The thin film is coated. At this time, the material of the second ultrafine particles or the second thin film may be any material suitable for use as a microcapsule. For example, NaCl is used as the fine particles, and DLC is used as the material of the second ultrafine particles or the second thin film.

  The details of the method for coating the second ultrafine particles or the second thin film made of DLC are the same as the method for coating the ultrafine particles or the thin film in the case of the first microcapsule.

  Thereafter, the coated first and second ultrafine particles or the NaCl fine particles serving as the base of the first and second thin films are removed by dissolution, vaporization or the like. The details are the same as those of the first microcapsule.

  In this embodiment, a hydrocarbon-based gas is used as the gas used, but various hydrocarbon-based gases can be used as long as they contain at least carbon and hydrogen. For example, carbon and hydrogen It is also possible to use a compound gas containing only carbon, a gas containing carbon, hydrogen and oxygen, a gas containing carbon, hydrogen, oxygen, silicon, nitrogen, copper, silver, benzene, toluene, acetylene, or the like.

  In the present embodiment, a hydrocarbon gas pressure of 0.5 mTorr or more and 500 mTorr or less is used in the film forming conditions, but a more preferable gas pressure is 10 mTorr or more and 100 mTorr or less.

In this embodiment mode, it is preferable to use a power density with an RF output of 0.28 W / cm ² or more under film formation conditions.

  Further, as the flow rate of the hydrocarbon-based gas, various gas flow rates can be used as long as the gas flow rate can realize the above pressure.

  Note that the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention. For example, it is possible to appropriately change the film forming conditions for forming a thin film on the fine particles.

  Further, in Embodiment 7, a microcapsule manufacturing method using the plasma CVD apparatus shown in FIG. 8 is described. However, the present invention is not limited to this, and microcapsule manufacturing using another CVD apparatus is described. It is also possible to apply the present invention to a method. For example, the microcapsule can be manufactured using the CVD apparatus of FIG. 3, the CVD apparatus of FIG. 4, or the CVD apparatus of FIG.

It is a block diagram which shows the outline of the thermal CVD apparatus by Embodiment 1 which concerns on this invention. It is sectional drawing which shows an example of the coated fine particle which coat | covered the thin film on fine particle with the thermal CVD apparatus shown in FIG. (A) is sectional drawing which shows the outline of the thermal CVD apparatus by Embodiment 2 which concerns on this invention, (B) is sectional drawing along the 3B-3B line | wire shown to (A). (A) is sectional drawing which shows the outline of the thermal CVD apparatus by Embodiment 3 which concerns on this invention, (B) is sectional drawing along the 4B-4B line | wire shown to (A). FIG. 5 is a cross-sectional view illustrating an example of coated fine particles obtained by coating fine particles with a thin film using the thermal CVD apparatus illustrated in FIG. 4. It is a block diagram which shows the outline of the plasma CVD apparatus by Embodiment 4 which concerns on this invention. (A) is sectional drawing which shows the outline of the plasma CVD apparatus by Embodiment 5 which concerns on this invention, (B) is sectional drawing along the 7B-7B line | wire shown to (A). (A) is sectional drawing which shows the outline of the plasma CVD apparatus by Embodiment 6 which concerns on this invention, (B) is sectional drawing along the 8B-8B line shown to (A). It is a figure which shows an example of the Raman spectrum of a DLC film. It is a bar graph which shows the result of cell-adhesion evaluation, Comprising: Each of AI and TCD which coated PS and DLC in a dish, and a light absorbency (OD595 nm) are shown. It is a bar graph which shows the result of cytotoxicity evaluation, and shows the relationship between each of AI and TCD which coated PS and DLC in a dish, and the elution rate of LDH. It is a bar graph which shows the adsorption rate of the protein of the bottom face part (A to I and TCD which coated PS, DLC) in a dish. It is a graph which shows the relationship between RF output at the time of producing the sample which performs a Raman spectrum analysis, and B / A value. It is a Raman spectrum curve for demonstrating the definition of B / A value. It is a graph which shows the relationship between the RF output at the time of producing each sample, and the density of a DLC film. It is a graph which shows the anodic polarization measurement result of the sample which formed the DLC film into a film with 100 W RF output, and shows the relation between potential and current density. It is a graph which shows the anodic polarization measurement result of the sample which formed the DLC film into a film with 200 W RF output, and shows the relationship between an electric potential and a current density. It is a graph which shows the anodic polarization measurement result of Si base | substrate which has not formed the DLC film, and shows the relationship between an electric potential and a current density.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Powder (fine particle), 2 ... Container, 3 ... Chamber, 4 ... Heater, 5-11 ... Piping, 12 ... 1st valve, 13 ... 2nd valve, 14, 15 ... Mass flow controller (MFC), 16 ... Argon gas introduction mechanism, 17 ... thin film, 18 ... coated fine particle, 19 ... container, 20 ... chamber lid, 21 ... heater, 22 ... container, 23 ... coated fine particle, 24 ... gas shower electrode, 25 ... plasma power source, 26 ... vacuum Valve, 27 ... Mass flow controller (MFC), 28 ... Source gas generation source, 29, 30 ... Container, 31 ... Plasma power source, 32, 33 ... Switch, 110 ... Raman spectrum curve, 111 ... Mountain-shaped curve (G band) , 112 ... mountain-shaped curve (D band)

Claims (28)

A coated fine particle, wherein the surface of the fine particle is coated with ultrafine particles or a thin film having a particle diameter smaller than that of the fine particle by a CVD method. By rotating a container having a substantially circular internal cross-sectional shape about a direction perpendicular to the cross-section as a rotation axis, using the CVD method while stirring or rotating the fine particles in the container, A coated fine particle characterized in that the surface is coated with ultrafine particles or a thin film having a particle diameter smaller than that of the fine particles. By rotating a container having an internal cross-sectional shape of a polygon about a direction substantially perpendicular to the cross-section as a rotation axis, using the CVD method while stirring or rotating the fine particles in the container, A coated fine particle characterized in that the surface is coated with ultrafine particles or a thin film having a particle diameter smaller than that of the fine particles. Contains fine particles in a container,
A CVD film forming method characterized in that the surface of the fine particles is coated with ultrafine particles or a thin film having a particle diameter smaller than the fine particles by using a thermal CVD method or a plasma CVD method. The fine particles are contained in a container whose internal shape of a cross section substantially parallel to the direction of gravity is substantially circular,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has an ultrafine particle smaller than the fine particles. A CVD film forming method characterized by coating fine particles or a thin film. Fine particles are housed in a container having a polygonal internal shape with a cross section substantially parallel to the direction of gravity,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has an ultrafine particle smaller than the fine particles. A CVD film forming method characterized by coating fine particles or a thin film. A container for placing fine particles;
A chamber containing the container;
A heating mechanism for heating the fine particles placed on the container;
A gas introduction mechanism for introducing a source gas into the chamber;
Comprising
A CVD apparatus characterized in that the surface of the fine particles is coated with ultra fine particles or a thin film having a smaller particle diameter than the fine particles by using a thermal CVD method. A container containing fine particles, and a container having a substantially circular inner shape in a cross section substantially parallel to the direction of gravity;
A rotation mechanism that rotates the container about a direction substantially perpendicular to the cross section as a rotation axis;
A heating mechanism for heating the fine particles contained in the container;
A gas introduction mechanism for introducing a source gas into the container;
Comprising
By using the thermal CVD method while stirring or rotating the fine particles in the container by rotating the container using the rotating mechanism, the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles. A CVD apparatus characterized by: A container containing fine particles, the container having a polygonal internal shape in a cross section substantially parallel to the direction of gravity;
A rotation mechanism that rotates the container about a direction substantially perpendicular to the cross section as a rotation axis;
A heating mechanism for heating the fine particles contained in the container;
A gas introduction mechanism for introducing a source gas into the container;
Comprising
By using the thermal CVD method while stirring or rotating the fine particles in the container by rotating the container using the rotating mechanism, the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles. A CVD apparatus characterized by: A container for placing fine particles;
A chamber containing the container;
A gas introduction mechanism for introducing a source gas into the chamber;
An electrode disposed in the chamber and disposed to face the container;
Comprising
A CVD apparatus characterized in that the surface of the fine particles is coated with ultrafine particles or a thin film having a smaller particle diameter than the fine particles by using a plasma CVD method. A container containing fine particles, and a container having a substantially circular inner shape in a cross section substantially parallel to the direction of gravity;
A rotation mechanism that rotates the container about a direction substantially perpendicular to the cross section as a rotation axis;
An electrode disposed in the container;
A gas introduction mechanism for introducing a source gas into the container;
Comprising
By using the plasma CVD method while stirring or rotating the fine particles in the container by rotating the container using the rotating mechanism, the surface of the fine particles is coated with ultrafine particles or a thin film having a particle diameter smaller than the fine particles. A CVD apparatus characterized by: A container containing fine particles, the container having a polygonal internal shape in a cross section substantially parallel to the direction of gravity;
A rotation mechanism that rotates the container about a direction substantially perpendicular to the cross section as a rotation axis;
An electrode disposed in the container;
A gas introduction mechanism for introducing a source gas into the container;
Comprising
By using the plasma CVD method while stirring or rotating the fine particles in the container by rotating the container using the rotating mechanism, the surface of the fine particles is coated with ultrafine particles or a thin film having a particle diameter smaller than the fine particles. A CVD apparatus characterized by: The CVD apparatus according to claim 10, wherein the gas introduction mechanism has a mechanism for introducing a shower-like gas from the electrode into the container. The CVD apparatus according to any one of claims 10 to 12, further comprising a chamber that accommodates the container and a vacuum exhaust mechanism that exhausts the inside of the chamber. A microcapsule formed of ultrafine particles or a thin film made of DLC having excellent biocompatibility,
A microcapsule having a property that does not impair an original function of a living body or a living body component when introduced into a living body or brought into contact with a living body. First ultrafine particles or first thin film constituting the outer surface;
A microcapsule comprising a second ultrafine particle or a second thin film formed inside the first ultrafine particle or the first thin film,
The first ultrafine particles or the first thin film is made of DLC having excellent biocompatibility,
A microcapsule having a property that does not impair the original function of a living body or a living body component when introduced into a living body or brought into contact with a living body. By rotating a container having a substantially circular internal cross-sectional shape about a direction perpendicular to the cross section as a rotation axis, the CVD method is used while stirring or rotating the fine particles in the container. A microcapsule, wherein the surface is coated with ultrafine particles or a thin film having a particle diameter smaller than that of the fine particles, and the coated ultrafine particles or the fine particles as a matrix of the thin film are removed. By rotating a container having an internal cross-sectional shape of a polygon about a direction substantially perpendicular to the cross-section as a rotation axis, using the CVD method while stirring or rotating the fine particles in the container, A microcapsule, wherein the surface is coated with ultrafine particles or a thin film having a particle diameter smaller than that of the fine particles, and the coated ultrafine particles or the fine particles as a matrix of the thin film are removed. In claim 17 or 18, the ultrafine particles or the thin film is made of DLC having excellent biocompatibility,
A microcapsule having a property that does not impair the original function of a living body or a living body component when introduced into a living body or brought into contact with a living body. By rotating a container having a substantially circular internal cross-sectional shape about a direction perpendicular to the cross section as a rotation axis, the CVD method is used while stirring or rotating the fine particles in the container. The surface is coated with the first ultrafine particle or the first thin film having a particle diameter smaller than that of the fine particle, and by using the CVD method, the surface of the first ultrafine particle or the first thin film is made smaller than the fine particle. The second ultrafine particles or the second thin film having a small diameter are coated, and the coated first and second ultrafine particles or the fine particles forming the base of the first and second thin films are removed. A microcapsule characterized by the above. By rotating a container having an internal cross-sectional shape of a polygon about a direction substantially perpendicular to the cross-section as a rotation axis, using the CVD method while stirring or rotating the fine particles in the container, The surface is coated with the first ultrafine particle or the first thin film having a particle diameter smaller than that of the fine particle, and by using the CVD method, the surface of the first ultrafine particle or the first thin film is made smaller than the fine particle. The second ultrafine particles or the second thin film having a small diameter are coated, and the coated first and second ultrafine particles or the fine particles forming the base of the first and second thin films are removed. A microcapsule characterized by the above. In Claim 20 or 21, the second ultrafine particles or the second thin film comprises DLC having excellent biocompatibility,
A microcapsule having a property that does not impair the original function of a living body or a living body component when introduced into a living body or brought into contact with a living body. The fine particles are contained in a container whose internal shape of a cross section substantially parallel to the direction of gravity is substantially circular,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has an ultrafine particle smaller than the fine particles. Coating fine particles or thin films,
A method for producing a microcapsule, comprising removing the coated ultrafine particles or the fine particles serving as a matrix of a thin film. Fine particles are housed in a container having a polygonal internal shape with a cross section substantially parallel to the direction of gravity,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has an ultrafine particle smaller than the fine particles. Coating fine particles or thin films,
A method for producing a microcapsule, comprising removing the coated ultrafine particles or the fine particles serving as a matrix of a thin film. 25. The ultrafine particle or thin film according to claim 23 or 24, comprising DLC having excellent biocompatibility,
When coating the ultrafine particles or thin film, a hydrocarbon-based gas containing at least carbon and hydrogen is introduced into the container under a pressure of 0.5 mTorr or more and 500 mTorr or less, and an electrode connected to a high-frequency power source is disposed in the container. A method for producing a microcapsule, wherein the electrode is coated with a plasma CVD method by applying a high frequency power having a power density of 0.28 W / cm ² or more to the electrode. The fine particles are contained in a container whose internal shape of a cross section substantially parallel to the direction of gravity is substantially circular,
By using the CVD method while stirring or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, Coating one ultrafine particle or first thin film;
The fine particles coated with the first ultrafine particles or the first thin film are accommodated in a container having a substantially circular cross section substantially parallel to the direction of gravity,
By using the CVD method while stirring or rotating the fine particles in the container by rotating the container about the direction substantially perpendicular to the cross section, the first ultrafine particles or the first thin film Coating the surface with second ultrafine particles or second thin film having a particle diameter smaller than that of the fine particles,
A method for producing a microcapsule, comprising removing the coated first and second ultrafine particles or the fine particles serving as a matrix of the first and second thin films. Fine particles are housed in a container having a polygonal internal shape with a cross section substantially parallel to the direction of gravity,
By using the CVD method while agitating or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section as a rotation axis, the surface of the fine particles has a smaller particle diameter than the fine particles. Coating one ultrafine particle or first thin film;
The fine particles coated with the first ultrafine particles or the first thin film are accommodated in a container whose inner shape of a cross section substantially parallel to the direction of gravity is a polygon,
By using the CVD method while stirring or rotating the fine particles in the container by rotating the container about a direction substantially perpendicular to the cross section, the first ultrafine particles or the first thin film Coating the surface with second ultrafine particles or second thin film having a particle diameter smaller than that of the fine particles,
A method for producing a microcapsule, comprising removing the coated first and second ultrafine particles or the fine particles serving as a matrix of the first and second thin films. In Claim 26 or 27, the second ultrafine particles or the second thin film comprises DLC having excellent biocompatibility,
When coating the second ultrafine particles or the second thin film, a hydrocarbon-based gas containing at least carbon and hydrogen is introduced into the container under a pressure of 0.5 mTorr or more and 500 mTorr or less and connected to a high frequency power source. A method of manufacturing a microcapsule, comprising: placing the electrode in the container, applying a high frequency power having a power density of 0.28 W / cm ² or more to the electrode, and coating the electrode by a plasma CVD method.

Images